CN107534156A - Gas-diffusion electrode base material and its manufacture method - Google Patents
Gas-diffusion electrode base material and its manufacture method Download PDFInfo
- Publication number
- CN107534156A CN107534156A CN201680022919.8A CN201680022919A CN107534156A CN 107534156 A CN107534156 A CN 107534156A CN 201680022919 A CN201680022919 A CN 201680022919A CN 107534156 A CN107534156 A CN 107534156A
- Authority
- CN
- China
- Prior art keywords
- base material
- gas
- electrode base
- mpl
- diffusion electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/861—Porous electrodes with a gradient in the porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Abstract
The present invention provides the reduction that can suppress to block caused gas diffusibility from pore, suppresses the excellent gas-diffusion electrode base material of the discharge of the reduction and water of power generation performance to outside system.The present invention is a kind of gas-diffusion electrode base material, it is that have the gas-diffusion electrode base material of micro- porous layer (hereinafter referred to as MPL) in a surface configuration of electrode base material, thickness is less than more than 110 μm 240 μm, the section of gas-diffusion electrode base material is being divided into the part with MPL and the part without MPL, and by the part without MPL it is second-class be divided into the part (hereinafter referred to as CP1 sections) contacted with MPL and do not contacted with MPL part (hereinafter referred to as CP2 sections) when, the F/C ratios in CP1 sections are less than more than 0.03 0.10, the F/C ratios in CP2 sections are less than 0.03.Here, " F " represents the quality of fluorine atom, " C " represents the quality of carbon atom.
Description
Technical field
Fuel cell is to obtain make hydrogen and oxygen react the mechanism of energy caused by generation water in form of electricity, due to energy
Amount efficiency is high, and effluent only has water, therefore is expected to be used as clean energy resource.The present invention relates to the gas used in a fuel cell
Body diffusion electrode base material and its manufacture method, more particularly to it is among fuel cell, make as the power supply of fuel-cell vehicle etc.
Gas-diffusion electrode base material and its manufacture method used in polymer electrolyte fuel cell.
Background technology
Electrode used in polymer electrolyte fuel cell, have on the two sides of polyelectrolyte membrane and be formed from height
The structure that the catalyst layer on polymeric electrolyte film surface and the gas diffusion layers formed in the outside of the catalyst layer are formed.Make
It is general extensively for the independent component for forming the gas diffusion layers in electrode, electrode base material.Moreover, as to the electrode base
Material requirement performance, such as can enumerate gas diffusibility, for by the electric conductivity of caused electric current collection in catalyst layer and will
In drainage removed to moisture excellent in efficiency caused by catalyst layer surface etc..In order to obtain such electrode base material, usually
Use the conductive porous matter base material for possessing gas diffusibility and electric conductivity.
As conductive porous matter base material, specifically, carbon felt, carbon paper and carbon cloth being made up of carbon fiber etc. can be used,
Wherein, from mechanical strength etc., most preferably carbon paper.
In addition, fuel cell is to obtain the system in energy caused by hydrogen and oxygen reaction generation water in form of electricity, because
This is when electric loading becomes big, i.e. when the electric current that increase obtains to outside batteries, can produce substantial amounts of water (vapor), the water
Steam condenses and is changed into water droplet at low temperature, if blocking the pore of gas diffusion layers, gas (oxygen or hydrogen) is to catalyst layer
Quantity delivered reduce, if final whole pore is blocked, generating can stop.The phenomenon is referred to as water logging.
In order to avoid occurring the water logging as far as possible, cause the current value of water logging conversely speaking, in order to increase as far as possible, to gas
Body diffused layer requires drainage.As the means for improving the drainage, hate usually using being implemented to conductive porous matter base material
The electrode base material of water process improves hydrophobicity.
In addition, it is proposed that by the amount of the hydrophobic material in electrode base material from catalyst layer side towards opposite side continuity
Ground is reduced, come the technology for making drainage further improve.(patent document 1,2)
Citation
Patent document
Patent document 1:No. 5079195 publications of Japanese Patent No.
Patent document 2:JP 2014-63730 publications
The content of the invention
In patent document 1, in order to only suppress infiltration of the hydrophobic liquid to electric conductivity Porous base material, it is proposed that while will lead
Electrical Porous base material heating is while the method for coating hydrophobic liquid.But if while conductive porous matter base material is heated one
Side applies hydrophobic liquid, then the amount of the hydrophobic material of the catalyst layer side of conductive porous matter base material becomes insufficient, in hydrophobicity
The position water-setting of shortage gathers, and hinders discharge of the water to outside system.
In patent document 2, it is proposed that apply from the one side of conductive porous matter base material and be made up of carbon dust and hydrophobic material
Coating liquid, the method for making the hydrophobic material in coating liquid penetrate into conductive porous matter base material.Propose：To conductive porous
Matter base material makes surfactant solution infiltrate conductive porous matter base without the situation of any processing and as base treatment
Material, coating liquid is set to be easier situation about penetrating into conductive porous matter base material.But the not only hydrophobic material in coating liquid,
Carbon dust is also penetrated into conductive porous matter base material, and thus, pore is blocked, and gas diffusibility reduces, and power generation performance reduces.Separately
Outside, in the case of having carried out base treatment especially with surfactant, hydrophobic material be present and carbon dust is reached and is coated with
The opposite side of that side of liquid is applied, the problem of hindering discharge of the water to outside system.
The present invention employs following scheme to solve above-mentioned problem.
A kind of gas-diffusion electrode base material, it is to have micro- porous layer (hereinafter referred to as in a surface configuration of electrode base material
MPL gas-diffusion electrode base material),
Thickness is less than more than 110 μm 240 μm,
The section of gas-diffusion electrode base material is being divided into the part with MPL and the part without MPL, and will not
Part with MPL is second-class to be divided into the part (hereinafter referred to as CP1 sections) contacted with MPL and the part not contacted with MPL (below
Referred to as CP2 sections) when, the F/C ratios in CP1 sections are less than more than 0.03 0.10, and the F/C ratios in CP2 sections are less than 0.03,
Wherein, F represents the quality of fluorine atom, and C represents the quality of carbon atom.
The fuel cell of gas diffusion layers is constituted using the gas-diffusion electrode base material of the present invention, in the low of fuel cell
Warm condition, the power generation performance i.e. under the high current density under conditions of fuel battery inside Water vapor condensation produces water droplet are good
It is good.
Brief description of the drawings
Fig. 1 is the pattern sectional view of the gas-diffusion electrode base material of the present invention.
Fig. 2 is that the part with MPL of the gas-diffusion electrode base material of the present invention and the portion boundary without MPL are said
Bright figure.
Embodiment
The gas-diffusion electrode base material of the present invention, has micro- porous layer (hereinafter referred to as in a surface configuration of electrode base material
MPL)。
Furthermore the base material for having MPL in electrode base material surface configuration in the present invention, is referred to as " gas diffusion electricity
Pole base material "." gas-diffusion electrode base material " is the individual member suitable with the gas diffusion layers in fuel cell electrode.Moreover,
" electrode base material " means " conductive porous matter base material " containing fluorine atom.
In the present invention, gas diffusion layers need：For the high gas that will be spread from the gas that dividing plate supplies to catalyst
The high drainage and produced for obtaining that body diffusivity, the water for will be generated along with electrochemical reaction are discharged to dividing plate
The high electric conductivity of raw electric current.Therefore, as electric used in the gas-diffusion electrode base material of gas diffusion layers for forming
Pole base material, use is conductive and average pore diameter is usually conductive porous that 10~100 μm of porous body is formed
Matter base material.
Here, as conductive porous matter base material, specifically, such as carbon fibre fabric, carbon fiber copy paper are preferably used
The Porous base material containing carbon fiber of body, carbon fiber nonwoven fabric, carbon felt, carbon paper, carbon cloth etc., foam sintering metal, wire netting,
The metal porous matter base material of XPM etc..Wherein, it is excellent as conductive porous matter base material from excellent corrosion resistance
Choosing uses the Porous base material containing carbon fiber, and then, characteristic from the change in size of the thickness direction of absorbed electrolyte film, i.e.
" elasticity " is excellent to set out, and is preferably used as bonding in carbon fiber copy paper body carbide the carbon paper of the base material formed.In this hair
In bright, carbon paper can be by infiltrating resin to carbon fiber copy paper body and being carbonized to obtain.
As carbon fiber, the carbon fiber of polyacrylonitrile (PAN) system, asphalt series, artificial silk system etc. can be enumerated.Wherein, slave
Tool excellent strength sets out, in the present invention preferably using PAN systems, pitch-based carbon fiber.
In the present invention, conductive porous matter base material, the thickness of electrode base material are preferably less than 210 μm.In addition, electric conductivity
Porous base material, the thickness of electrode base material are preferably more than 90 μm.When the thickness of conductive porous matter base material, electrode base material is
At less than 210 μm, in the case where using it as gas-diffusion electrode base material, the diffusion length of the gas of thickness direction becomes
Short, gas diffusibility improves, further, since the path of draining shortens, therefore drainage improves, and can suppress water logging, moreover, leading
The path of electricity shortens, and electric conductivity improves, no matter power generation performance all improves in the case of which kind of of high temperature and low temperature.
On the other hand, when the thickness of conductive porous matter base material, electrode base material is more than 90 μm, from conductive porous
When one surface of matter base material carries out hydrophobic processing, do not oozed out in another face hydrophobic material, the F/C ratios in CP2 sections are changed into
Less than 0.01, so as to which water droplet is smoothly discharged outside system, therefore drainage improves, and can suppress water logging, therefore in low temperature
Under power generation performance improve.In addition, when the thickness of conductive porous matter base material, electrode base material is more than 90 μm, it is being used
In the case of as gas-diffusion electrode base material, the gas diffusibility in direction improves in face, and gas is under the rib of dividing plate
The supply of catalyst also can be carried out more easily, no matter therefore power generation performance all carries in the case of which kind of of high temperature and low temperature
It is high.In addition, when the thickness of conductive porous matter base material, electrode base material is more than 90 μm, the machinery of conductive porous matter base material
Intensity more improves, in the case where using it as gas-diffusion electrode base material, easy support electrolyte plasma membrane, catalyst layer.
Here, conductive porous matter base material, the thickness of electrode base material, can be in the state pressurizeed with surface pressure 0.15MPa
It is lower to be tried to achieve using micrometer.Value is as conductive porous matter base obtained from being averaged to each measured value at 10 positions
The thickness of material or electrode base material.
In the present invention, according to as foregoing, the conductive porous matter base material containing fluorine atom is electrode base material.Cause
This, such as by assigning fluororesin to conductive porous matter base material, can be formed as the conductive porous matter containing fluorine atom
The electrode base material of base material.Here, the fluorine atom of fluororesin etc. plays a role as hydrophobic material.Furthermore conductive porous matter base
Whether material contains fluorine atom, that is to say, that whether some base material passes through the F/C in described later CP1 section equivalent to electrode base material
Than, CP2 sections F/C than any one of at least whether big among the F/C ratios on the surface of, the opposite side in that side with being configured with MPL
Judged in 0.
In order to obtain electrode base material, it is suitable for the fluororesin assigned to conductive porous matter base material, PTFE (poly- four can be enumerated
PVF) (such as " テ Off ロ Application " (registration mark)), FEP (tetrafluoraoethylene-hexafluoropropylene copolymer), PFA (perfluoro alkoxies
Fluoride resin), ETFA (ethylene-tetrafluoroethylene copolymer), PVDF (polyvinylidene fluoride), PVF (polyvinyl fluoride) etc..Wherein,
It is preferred that use the fluororesin that fusing point is less than more than 200 DEG C 320 DEG C.If fluororesin as use, fluororesin is dissolving
Shi Bianwei low viscosities, the segregation of the segregation of fluororesin, i.e. fluorine atom tail off, and have used the gas diffusion electricity of such electrode base material
The power generation performance of pole base material improves.As the fluororesin that fusing point is less than more than 200 DEG C 320 DEG C, FEP or PFA can be enumerated, especially
Preferably FEP.
Electrode base material in the gas-diffusion electrode base material of the present invention, the amount of the amount of hydrophobic material, i.e. fluorine atom, from catalysis
Reduced towards opposite side continuity oxidant layer side.That is, the gas-diffusion electrode base material of the present invention, according to shown in Fig. 1
Like that, the section of gas-diffusion electrode base material 1 is being divided into the part (MPL2) with MPL and the part (electrode without MPL
Base material 3), moreover, being divided into the part without MPL is second-class the part (CP1 sections 4) contacted with MPL and not contacted with MPL
Partly when (CP2 sections 5), the F/C ratios in CP1 sections are less than more than 0.03 0.10, and the F/C ratios in CP2 sections are less than 0.03, preferably
The F/C ratios in CP2 sections are less than 0.01.Here, " F " represents the quality of fluorine atom, " C " represents the quality of carbon atom.CP2 sections
F/C than lower limit be 0.
In addition, for making the F/C in CP2 sections, than the method less than 0.03, there is no particular limitation.For example, by from thickness
Hydrophobic material is applied for the side of more than 90 μm of conductive porous matter base materials, the F/C ratios in CP2 sections can be made to be less than 0.03.
Making the F/C in CP1 sections, there is no particular limitation than the method for less than more than 0.03 0.10.For example, by that will make
The coating amount of the fluororesin used for hydrophobic material is set to 1~5 mass parts relative to the mass parts of conductive porous matter base material 100,
The F/C ratios that CP1 sections can be made are less than more than 0.03 0.10.
F/C ratios are the indexs of the amount of the fluororesin for the hydrophobic material for being denoted as bringing hydrophobicity.F/C than it is big when hate
Water-based height.If the F/C ratios in CP1 sections are more than 0.03, with sufficient hydrophobicity, water droplet can be prevented to be stranded in CP1.Separately
Outside, if the F/C ratios in CP1 sections be less than 0.10, will will not occur in catalyst layer surface and by MPL towards CP1 and
The water droplet come pushes back, and is discharged to after entering in electrode base material outside system.If the F/C ratios in CP2 sections are less than 0.03, can incite somebody to action
From CP1 towards CP2, next water droplet is discharged to outside system.When for more than 0.03 when, hydrophobic material can hinder water droplet to outside system
Discharge, drainage reduce.
Here, when the section of gas-diffusion electrode base material to be divided into part with MPL and the part without MPL,
In a manner of the front end of the part in electrode base material is most penetrated into comprising MPL, it can be put down as shown in Figure 2 with the surface of base material
Rule capablely to determine.Details is described below.
If the F/C ratios on the surface of gas-diffusion electrode base material, with being configured with MPL the opposite side in that side of the present invention are
Less than 0.01, then can by from CP1 towards CP2 and the water droplet that comes is discharged to outside system, therefore preferably.That side with being configured with MPL
The F/C on the surface of opposite side than lower limit be 0.
The F/C on the surface of the opposite side in that side for making with being configured with MPL is not more special than the method for less than 0.01
Limit.For example, the method that hydrophobic material is applied from the side of the conductive porous matter base material of more than 90 μm of thickness can be used.
If the F/C ratios on the surface of that side for being configured with MPL of the gas-diffusion electrode base material of the present invention are more than 0.10,
Then there is sufficient hydrophobicity, water droplet can be prevented to be stranded in MPL, therefore preferably.In addition, if it is configured with the table of MPL that side
The F/C ratios in face be less than 0.40, then will not push back from catalyst towards MPL and come water droplet, hydropexis can be prevented in catalyst
Between layer and MPL, therefore preferably.In order that the F/C ratios on the surface of that side for being configured with MPL of gas-diffusion electrode base material are
Less than more than 0.10 0.40, such as the method for making MPL contain fluororesin can be enumerated.
The gas-diffusion electrode base material of the present invention, has MPL in a surface configuration of electrode base material.
MPL has：For the high gas perpendicular to the direction on surface that will be spread from the gas that dividing plate supplies to catalyst
High drainage that body diffusivity, the aqueous water for will be generated along with electrochemical reaction are discharged to dividing plate, for obtaining
The high electric conductivity of caused electric current.Moreover, MPL, which also has, promotes counter diffusion of the moisture to dielectric film, dielectric film is wet
The function of profit.In the present invention, the surface that MPL is only configured at electrode base material is critically important.If MPL is configured at electrode
The two sides of base material, then it is changed between electrode base material and dividing plate also configuring the high MPL of hydrophobicity, therefore can hinders from electrode base material
Internal drainage, power generation performance at low temperature reduce.
There is no particular limitation for the manufacture method of the gas-diffusion electrode base material of the present invention.Particularly preferably：With from conduction
Property Porous base material the dispersion liquid of a surface spray or coating containing fluororesin, also, after the process, on the surface
Configure MPL manufacture method.The manufacture method of the gas-diffusion electrode base material of the present invention is illustrated below.
The electrode base material of the present invention, is the conductive porous matter base material containing fluorine atom.It can be by implementing to electric conductivity
The so-called hydrophobic that Porous base material assigns hydrophobic material is handled to obtain.Hydrophobic processing, can be by from conductive porous matter base
Dispersion liquid of the surface coating containing above-mentioned fluororesin of material, is then heat-treated to carry out.Painting as hydrophobic material
Apply, it is preferred to use spraying, the coating using the progress such as die coating machine of the progress such as sprayer.The coating of fluororesin during hydrophobic processing
Amount, is 1~5 mass parts preferably with respect to the mass parts of conductive porous matter base material 100.When the coating amount of fluororesin is 1 mass parts
During the above, electrode base material turns into the excellent base material of drainage, therefore preferably.In addition, when fluororesin coating amount for 5 mass parts with
When lower, electrode base material turns into the base material of excellent electric conductivity, therefore preferably.Apply fluororesin after, preferably 90 DEG C less than
It is dried at a temperature of 200 DEG C.For the gas-diffusion electrode base material of the present invention, preferably in this wise from conductive porous matter base
After one surface of material has carried out hydrophobic processing, in surface configuration MPL manufacture method.
MPL includes carbon black, CNT, carbon nano-fiber, chopped strand (chopped fiber), the graphite of carbon fiber
The conductive particle of alkene, graphite etc..As conductive particle, particularly preferably using carbon black, CNT, carbon Nanowire
Dimension, graphene.As carbon black, from impurity it is few, be difficult to the aspect that reduces the activity of catalyst, preferably using acetylene black.
In addition, MPL requires electric conductivity, gas diffusibility, the drainage of water or moisture retention, heat conductivity so
Characteristic and fuel battery inside the resistance to highly acid of anode-side, the oxidative resistance of cathode side.Therefore, MPL preferably except containing
Beyond conductive particulate, also containing the hydrophobicity resin headed by fluororesin.As the fluororesin used in MPL, with
The fluororesin used in electrode base material similarly preferred PTFE, FEP, PFA, ETFA etc..From hydrophobicity highest aspect,
It is preferred that PTFE.It it is 330 DEG C or so but PTFE fusing point is higher, therefore also having must make sintering temperature described later be 350 DEG C
The shortcomings that above.In view of the point, the fluororesin that the fusing points such as FEP are less than 300 DEG C is also recommended.As the lower limit of fusing point,
It is essentially 100 DEG C or so more than the boiling point of solvent, preferably more than 150 DEG C.
In order to set MPL to electrode base material, the masking liquid of MPL formation is usually applied on a surface of electrode base material
(hereinafter referred to as MPL masking liquids).MPL masking liquids usually contain the solvent of above-mentioned conductive particle, He Shui, alcohol etc., coordinate and are used for
The situation of the surfactant that conductive particle is disperseed etc. is more.In addition, in order that MPL contains hydrophobicity resin, in advance
Coordinate hydrophobicity resin to MPL masking liquids.
Coating of the MPL masking liquids to electrode base material, commercially available various applying devices can be used to carry out.It is used as coating side
Formula, can be used screen painting, rotary screen painting, sprayer spraying, intaglio printing, photogravure, die coating machine apply,
Rod applies, scraper plate applies etc..The quantification of coating amount can be sought due to being not dependent on the surface roughness of electrode base material, therefore
It is preferred that the coating carried out using die coating machine.The coating method illustrated above is to illustrate after all, is not necessarily limited to these
Coating method.
After MPL masking liquids are applied, for remove for conductive particle scattered surfactant purpose and
The purpose for once melting fluororesin and bonding conductive particle, is sintered.On the temperature of sintering, than surface-active
Carried out at the boiling point or decomposition temperature of agent and the high temperature of the fusion temperature of fluororesin.In the case of using PTFE, due to it
Fusing point is 330 DEG C or so, therefore burnt with more than 330 DEG C, preferably more than 350 DEG C of sintering temperature, the condition of more than 30 seconds
Become.But if sintering temperature is too high, it is likely that fluororesin is decomposed, therefore usual 400 DEG C or so are the upper limit.
In addition, on sintering time, from the viewpoint of productivity ratio, usual 60 points or so are the upper limit.
As surfactant, from the few aspect of impurity, the general surfactant for using nonionic system.It can be used
Octylphenoxy polyethoxy ethanol (" TRITON (registration mark) " X-100 Na カ ラ イ テ ス Network (strain) system etc.), polyoxy second
Allylic alkylation ether, polyvinyl alcohol etc..
Among the surface of the both sides of electrode base material, preferably section F/C than being set for less than more than 0.03 0.10 CP1 sides
Put MPL.That is, in the preferable manufacture method of the present invention, preferably：With a table from conductive porous matter base material
The process of dispersion liquid of the face coating containing above-mentioned fluororesin, also, after the process, from that side on the surface, coating MPL is applied
Liquid.In a fuel cell, produced by reaction and the moisture generated in catalyst layer.That is, in gas-diffusion electrode base material,
Moisture is produced setting MPL that side.In caused hydrogenesis as in the case of water droplet, water droplet is from the high area of hydrophobicity
Moved to the low region of hydrophobicity in domain.Therefore, that high side of the hydrophobicity of electrode base material surface set MPL when, easily to
Water droplet caused by bulkhead sides exclusion, therefore preferably.
In the present invention, the thickness of gas-diffusion electrode base material is less than 240 μm.In addition, gas-diffusion electrode base material
Thickness is more than 110 μm.When the thickness of gas-diffusion electrode base material is less than 240 μm, the diffusion of the gas of thickness direction away from
From shortening, gas diffusibility improves, further, since the path of draining shortens, therefore drainage improves, and can suppress water logging, and
And conductive path shortens, electric conductivity improves, no matter power generation performance all improves in the case of which kind of of high temperature and low temperature.It is another
Aspect, when the thickness of gas-diffusion electrode base material is more than 110 μm, the gas diffusibility in direction improves in face, can be more
Easily to the catalyst supply gas under the rib in dividing plate, no matter therefore the generating property in the case of which kind of of high temperature and low temperature
Can all it improve.
The gas-diffusion electrode base material having a thickness that, can by control conductive porous matter base material thickness and
MPL thickness obtains.Here, the thickness of gas-diffusion electrode base material, can be in the state of having been pressurizeed with surface pressure 0.15MPa
Tried to achieve using micrometer, averagely resulting value is carried out as gas-diffusion electrode base material using to each measured value at 10 positions
Thickness.
In the present invention, the gas diffusibility of the thickness direction of gas-diffusion electrode base material is preferably more than 30%.Work as gas
When body diffusivity is more than 30%, no matter high power generation performance can be obtained in the case of which kind of of high temperature and low temperature.Thickness side
To gas diffusibility it is the higher the better.But when group enters fuel cell, if voidage is too high, in fuel cell
When portion is applied with pressure, become unable to enough its structures of maintenance, it can be considered that the higher limit of gas diffusibility is 40% or so.
In order that the gas diffusibility of the thickness direction of gas-diffusion electrode base material be more than 30%, for example, can enumerate by
The method that the thickness of the electrode base material used is set to less than 210 μm.
The gas-diffusion electrode base material of the present invention, in a manner of the MPL of catalyst layer and gas-diffusion electrode base material is contacted
The both sides for the dielectric film that catalyst layer is provided with two sides are crimped on, and then the component of dividing plate etc. is loaded to assemble single electricity
Pond, used as fuel cell.
Embodiment
Further illustrate the present invention by the following examples.The material used in embodiment and comparative example is illustrated below
Material, various evaluation methods.
The making ＞ of ＜ electrode base materials
By carbonized polyacrylonitrile fibre " ト レ カ " (registration mark) T300 (average carbon fiber diameters of eastern beautiful (strain) system：7μ
M) average length 12mm is cut into, is dispersed in water it, using wet type copy paper method come continuously copy paper.And then bonding will be used as
The 10 mass % aqueous solution of the polyvinyl alcohol of agent are coated on the copy paper, are dried, produce copy paper body.The coating of polyvinyl alcohol
Amount, is 22 mass parts relative to the mass parts of copy paper body 100.
Used as thermosetting resin by solvable phenolic aldehyde (resol) type phenolic resin and novolaks
(novolac) type phenolic resin is with 1：The resin that 1 mass ratio mixes, flakey is used as carbon system filler
Graphite (5 μm of average grain diameter), methanol is used as solvent, with the mass of mass parts of thermosetting resin/carbon system filler/solvent=10/5
Part/85 match ratios of mass parts they are mixed, the stirring of 1 minute is carried out using ultrasonic wave distributing device, has been obtained equably
Scattered resin combination.
The copy paper body for being cut into 15cm × 12.5cm is impregnated in the resin combination filled in Aluminum Drum, infiltrated so that
Obtain relative to the mass parts of carbon fiber 100, resin component (thermosetting resin+carbon system filler) turns into 130 mass parts, then, 100
5 minutes are heated at DEG C to be dried, produces preimpregnation body.Secondly, while being pressurizeed using Flat pressure machine, while
The heat treatment of 5 minutes has been carried out at 180 DEG C.Furthermore in pressurization, Flat pressure machine configuration space part (spacer) is adjusted
The interval of upper and lower pressing panel.
Base material obtained from being heat-treated to preimpregnation body imported into heating furnace the highest for being kept into nitrogen atmosphere
Temperature is in 2400 DEG C of heating furnace, obtains conductive porous matter base material.
Sprayed using sprayer from a face of conductive porous matter base material with vaporific relative to conductive porous matter base material
99 mass parts are FEP (" ネ オ Off ロ Application " (registration mark) ND- of ダ イ キ Application Industrial Co., Ltd of 1 mass parts
110) 5 minutes, are heated at 100 DEG C to be heat-treated, produces the electrode base material of 160 μm of thickness.
＜ MPL formation ＞
Using seam die coating machine, MPL is formd in being coated with FEP face for electrode base material.Applied for MPL as used herein
Liquid, a kind of acetylene black (" デ Application カ Block of electrochemical industry Co. Ltd. system as carbon black is used as conductive particle
ラ ッ Network " (registration mark)), use PTFE (" Port リ Off ロ Application " (registrations of ダ イ キ Application Industrial Co., Ltd as fluororesin
Trade mark) D-1E), " TRITON " (registration mark) X- of Na カ ラ イ テ ス Network Co. Ltd. systems is used as surfactant
100, use purified water as decentralized medium.It is adjusted, coordinates so as to the mass parts of conductive particle 7.7, fluorine
The mass parts of resin 4, the mass parts of surfactant 14, the mass parts of decentralized medium 74.3.MPL is applied to electrode base material using die coating machine
After masking liquid, 5 minutes, heating (sintering) 10 minutes at 380 DEG C are heated at 100 DEG C, produce the gas diffusion of 194 μm of thickness
Electrode base material.
The F/C of ＜ gas-diffusion electrode base materials is than measure ＞
The surface of that side for being configured with MPL of gas-diffusion electrode base material is determined as described below and with being configured with MPL
The opposite side in that side surface F/C ratios.
Gas-diffusion electrode base material is cut into 5 × 5mm.Using SEM-EDX (energy dispersion type fluorescent x-ray), 5 will be cut into
A part for × 5mm gas-diffusion electrode base material is amplified to 200 times.In accelerating potential 5KeV, 20 μm of sweep length, line scanning
The elementary analysis on the surface of desired measure has been carried out under 50 μm of interval.X-ray amount (count number) corresponding with fluorine and carbon is quantified,
Obtain F/C ratios.
In addition, the F/C ratios in the section of gas-diffusion electrode base material are determined as described below.
Gas-diffusion electrode base material is horizontal positioned, with respect to the horizontal plane vertically cut into slices, revealed using single-point tool
Section is gone out.Using SEM-EDX (energy dispersion type fluorescent x-ray), and enlargement ratio is have adjusted to cause from close to a table
The visual field (overall visual field) of the part in face to the part close to another surface is in monitor picture.In accelerating potential
The elementary analysis in the section of gas-diffusion electrode base material has been carried out under 5KeV, 20 μm of sweep length, 50 μm of line sweep spacing.Will be with
X-ray amount (count number) corresponding to fluorine and carbon is quantitative, obtains F/C ratios.
Furthermore on section F/C than measure, among the section of gas-diffusion electrode base material without MPL
Part is that CP1 sections and CP2 sections are carried out respectively.Here, as shown in Figure 2, part with MPL with without MPL's
Portion boundary 6 is set to：It is parallel with the surface of base material in a manner of the front end of the part in electrode base material is most penetrated into comprising MPL
The line that ground marks.
Furthermore as SEM-EDX, use and energy dispersion type fluorescence X is addition of in the SEM H-3000 of Hitachi
Line analysis device SEMEDEX Type-H device.
The gas diffusibility evaluation ＞ of ＜ thickness directions
The gaseous vapor of Xihua industry has been used through diffusion evaluating apparatus (MVDP-200C).To gas diffusion electricity
The diffusible gas of measure is wanted in side (the 1 side) circulation of pole base material, and to opposite side (2 sides), circulated nitrogen.By 1 side
Controlled with the pressure difference of 2 sides near 0Pa (0 ± 3Pa).That is, it is configured in advance：The almost not no gas as caused by pressure differential
Flowing, the state of the mobile phenomenon of gas is only caused by molecule diffusion.Gas concentration meter using 2 sides reaches to determine
Gas concentration during balance, the gas diffusibility using resulting value (%) as thickness direction.
＜ power generation performances evaluate ＞
Make resulting gas-diffusion electrode base material, dielectric film-catalysis is clamped in a manner of catalyst layer and MPL contact
Oxidant layer integration product (form Japanese go ア on the two sides of Japanese go ア dielectric film " go ア セ レ Network ト (registration mark) "
Catalyst layer " PRIMEA (registration mark) " product obtained from of system) both sides, and carry out hot pressing, thus make membrane electricity
Pole conjugant (MEA).The membrane-electrode assembly group is entered into fuel cell monomeric unit, makes battery temperature for 57 DEG C, combustion
Material utilization ratio is 70%, air utilization ratio is 40% and makes the hydrogen of anode-side, each dew point turns into 57 to the air of cathode side
DEG C, 57 DEG C humidified so as to be generated electricity.It is 1.9A/cm by current density2When output voltage as resistance to water logging
Index.
(embodiment 1)
According to the method described in the making ＞ and ＜ MPL of ＜ electrode base materials formation ＞, gas-diffusion electrode has been obtained
Base material.The power generation performance of the gas-diffusion electrode base material is have rated, as a result as described in table 1, output voltage 0.40V
(57 DEG C of running temperature, 57 DEG C of humidification temperature, current density 1.9A/cm2), resistance to water logging is also good.Other measurement results please
The record being shown in Table in 1.
(embodiment 2)
In the making ＞ of ＜ electrode base materials, using sprayer from a face of conductive porous matter base material with vaporific spraying
Relative to the FEP that the mass parts of conductive porous matter base material 95 are 5 mass parts, 5 minutes are heated at 100 DEG C to be heat-treated,
So as to produce electrode base material, in addition, according to the side described in the making ＞ and ＜ MPL of ＜ electrode base materials formation ＞
Method, gas-diffusion electrode base material is obtained.The power generation performance of the gas-diffusion electrode base material is have rated, as a result as described in table 1
As, output voltage is 0.42V (57 DEG C of running temperature, 57 DEG C of humidification temperature, current density 1.9A/cm2), resistance to water logging
Well.Other measurement results are see the record in table 1.
(embodiment 3)
In the making ＞ of ＜ electrode base materials, using die coating machine from the coating of a face of conductive porous matter base material relative to
The mass parts of conductive porous matter base material 95 are the FEP of 5 mass parts, are heat-treated 5 minutes at 100 DEG C, so as to produce electrode base
Material, in addition, according to the method described in the making ＞ and ＜ MPL of ＜ electrode base materials formation ＞, gas diffusion is obtained
Electrode base material.The power generation performance of the gas-diffusion electrode base material is have rated, as a result as described in table 1, output voltage is
0.41V (57 DEG C of running temperature, 57 DEG C of humidification temperature, current density 1.9A/cm2), resistance to water logging is also good.Others measure knot
Fruit is see the record in table 1.
(embodiment 4)
In the making ＞ of ＜ electrode base materials, using die coating machine from the coating of a face of conductive porous matter base material relative to
The mass parts of conductive porous matter base material 93 are the FEP of 7 mass parts, are heat-treated 5 minutes at 100 DEG C, so as to produce electrode base
Material, in addition, according to the method described in the making ＞ and ＜ MPL of ＜ electrode base materials formation ＞, gas diffusion is obtained
Electrode base material.The power generation performance of the gas-diffusion electrode base material is have rated, as a result as described in table 1, output voltage is
0.40V (57 DEG C of running temperature, 57 DEG C of humidification temperature, current density 1.9A/cm2), resistance to water logging is also good.Others measure knot
Fruit is see the record in table 1.
(comparative example 1)
In the making ＞ of ＜ electrode base materials, processed without hydrophobic, be not in electrode base in ＜ MPL formation ＞
One face of material, but MPL is formd in a face of conductive porous matter base material, in addition, according to ＜ electrode base materials
The method described in ＞ and ＜ MPL formation ＞ is made, has obtained gas-diffusion electrode base material.It has rated the gas-diffusion electrode
The power generation performance of base material, it is that output voltage is 0.38V (57 DEG C of running temperature, humidification temperature as a result as described in table 1
57 DEG C, current density 1.9A/cm2), the slightly worse result of resistance to water logging.Other measurement results are see the record in table 1.
(comparative example 2)
In the making ＞ of ＜ electrode base materials, using FEP relative to the mass parts of conductive porous matter base material 99 as 1 mass parts
Mode is implemented to infiltrate hydrophobic, and 5 minutes are heated at 100 DEG C to be dried, so as to produce electrode base material, in addition, is pressed
According to the method described in the making ＞ and ＜ MPL of ＜ electrode base materials formation ＞, gas-diffusion electrode base material has been obtained.It has rated
The power generation performance of the gas-diffusion electrode base material, it is that output voltage is 0.35V (running temperatures as a result as described in table 1
57 DEG C, 57 DEG C of humidification temperature, current density 1.9A/cm2), the slightly worse result of resistance to water logging.Other measurement results are see table 1
In record.
(comparative example 3)
In the making ＞ of ＜ electrode base materials, to Flat pressure machine configuration space part, it have adjusted between upper and lower pressing panel
Every so that the thickness of electrode base material turns into 70 μm, in addition, according to the making ＞ and ＜ MPL of ＜ electrode base materials formation ＞
Described in method, obtained gas-diffusion electrode base material.The power generation performance of the gas-diffusion electrode base material is have rated, as a result such as
It is that output voltage is 0.30V (57 DEG C of running temperature, 57 DEG C of humidification temperature, current density 1.9A/ as described in table 1
cm2), the slightly worse result of resistance to water logging.Other measurement results are see the record in table 1.
(comparative example 4)
In the making ＞ of ＜ electrode base materials, to Flat pressure machine configuration space part, it have adjusted between upper and lower pressing panel
Every so that the thickness of electrode base material turns into 230 μm, in addition, according to the making ＞ and ＜ MPL of ＜ electrode base materials formation ＞
Described in method, obtained gas-diffusion electrode base material.The power generation performance of the gas-diffusion electrode base material is have rated, as a result such as
It is that output voltage is 0.25V (57 DEG C of running temperature, 57 DEG C of humidification temperature, current density 1.9A/ as described in table 1
cm2), the slightly worse result of resistance to water logging.Other measurement results are see the record in table 1.
In table, " CP1F/C ratios " represents the F/C ratios in CP1 sections, and " CP2F/C ratios " represents the F/C ratios in CP2 sections, " MPL
Surface F/C ratios " expression " is configured with the F/C ratios on the surface of MPL that side, " MPL opposing faces F/C ratios " represents and be configured with MPL's
The F/C ratios on the surface of the opposite side in that side.
Description of reference numerals
1 gas-diffusion electrode base material
2 MPL
3 electrode base materials
4 CP1 sections
5 CP2 sections
6 parts with MPL and the portion boundary without MPL
Claims (7)
1. a kind of gas-diffusion electrode base material, expanded in the surface configuration gas that has the i.e. MPL of micro- porous layer of electrode base material
Dissipate electrode base material,
Thickness is less than more than 110 μm 240 μm,
The section of gas-diffusion electrode base material is being divided into the part with MPL and the part without MPL, and will not had
MPL part is second-class be divided into the part contacted with MPL i.e. CP1 sections and the part not contacted with MPL i.e. CP2 sections when, CP1 is cut
The F/C ratios in face are less than more than 0.03 0.10, and the F/C ratios in CP2 sections are less than 0.03,
Wherein, F represents the quality of fluorine atom, and C represents the quality of carbon atom.
2. gas-diffusion electrode base material according to claim 1, the F/C ratios in the CP2 sections are less than 0.01.
3. gas-diffusion electrode base material according to claim 1, the gas-diffusion electrode base material, with configuration MPL
The F/C ratios on the surface of the opposite side in that side are less than 0.01.
4. gas-diffusion electrode base material according to claim 1 or 2, the gas-diffusion electrode base material, configuration MPL
The F/C ratios on the surface of that side are less than more than 0.10 0.40.
5. the gas-diffusion electrode base material according to any one of claims 1 to 3, the gas diffusibility of thickness direction are
More than 30%.
6. a kind of manufacture method of gas-diffusion electrode base material, is the gas diffusion described in any one of manufacturing claims 1~5
The method of electrode base material, it is characterised in that
Including from a surface of conductive porous matter base material with it is vaporific spraying the dispersion liquid containing fluororesin process,
Also, after the process, in surface configuration MPL.
7. a kind of manufacture method of gas-diffusion electrode base material, is the gas diffusion described in any one of manufacturing claims 1~5
The method of electrode base material, it is characterised in that
Process including applying the dispersion liquid containing fluororesin from a surface of conductive porous matter base material,
Also, after the process, in surface configuration MPL.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-089039 | 2015-04-24 | ||
| JP2015089039 | 2015-04-24 | ||
| PCT/JP2016/062149 WO2016171082A1 (en) | 2015-04-24 | 2016-04-15 | Gas-diffusion electrode base material and method for manufacturing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107534156A true CN107534156A (en) | 2018-01-02 |
| CN107534156B CN107534156B (en) | 2020-11-27 |
Family
ID=57144445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680022919.8A Active CN107534156B (en) | 2015-04-24 | 2016-04-15 | Gas diffusion electrode substrate and method for producing same |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US10680250B2 (en) |
| EP (1) | EP3288106B1 (en) |
| JP (1) | JP6135826B2 (en) |
| KR (1) | KR102587488B1 (en) |
| CN (1) | CN107534156B (en) |
| CA (1) | CA2980461C (en) |
| ES (1) | ES2767928T3 (en) |
| TW (1) | TWI668908B (en) |
| WO (1) | WO2016171082A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7114858B2 (en) * | 2017-03-17 | 2022-08-09 | 東レ株式会社 | Gas diffusion electrode and fuel cell |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109604A (en) * | 2001-09-27 | 2003-04-11 | Matsushita Electric Ind Co Ltd | Gas diffusion electrode for fuel cell and method of manufacturing the same |
| CN101053101A (en) * | 2004-08-25 | 2007-10-10 | 通用汽车公司 | Diffusion media with microporous layer |
| CN103081194A (en) * | 2010-08-27 | 2013-05-01 | 东邦泰纳克丝株式会社 | Conductive sheet and production method for same |
| CN103563143A (en) * | 2011-06-17 | 2014-02-05 | 日产自动车株式会社 | Gas diffusion layer for fuel cell |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5324790Y2 (en) | 1973-11-21 | 1978-06-24 | ||
| JP4338491B2 (en) * | 2003-10-08 | 2009-10-07 | パナソニック株式会社 | Method for producing gas diffusion layer for polymer electrolyte fuel cell |
| EP2228857A1 (en) * | 2009-03-06 | 2010-09-15 | Basf Se | Improved membrane electrode units |
| KR102121822B1 (en) | 2012-08-24 | 2020-06-11 | 도레이 카부시키가이샤 | Gas-diffusion electrode base material for fuel cell |
| JP6183065B2 (en) | 2012-08-31 | 2017-08-23 | 三菱ケミカル株式会社 | Porous carbon electrode and manufacturing method thereof |
| US9806326B2 (en) * | 2013-12-05 | 2017-10-31 | GM Global Technology Operations LLC | One-step method for preparing a lithiated silicon electrode |
| CA2940184A1 (en) * | 2014-03-28 | 2015-10-01 | Toray Industries, Inc. | Gas diffusion electrode and method for manufacturing the same |
| EP3352269A4 (en) * | 2015-09-18 | 2019-03-20 | Toray Industries, Inc. | Gas diffusion electrode and method for producing same |
| US11016227B2 (en) * | 2017-09-18 | 2021-05-25 | Lumentum Operations Llc | Diffractive optical element |
| US10873083B2 (en) * | 2017-11-30 | 2020-12-22 | Global Graphene Group, Inc. | Anode particulates or cathode particulates and alkali metal batteries |
| US10637043B2 (en) * | 2017-11-30 | 2020-04-28 | Global Graphene Group, Inc. | Anode particulates or cathode particulates and alkali metal batteries containing same |
-
2016
- 2016-04-15 WO PCT/JP2016/062149 patent/WO2016171082A1/en active Application Filing
- 2016-04-15 EP EP16783103.1A patent/EP3288106B1/en active Active
- 2016-04-15 KR KR1020177032590A patent/KR102587488B1/en active IP Right Grant
- 2016-04-15 JP JP2016528913A patent/JP6135826B2/en active Active
- 2016-04-15 US US15/567,111 patent/US10680250B2/en active Active
- 2016-04-15 CN CN201680022919.8A patent/CN107534156B/en active Active
- 2016-04-15 CA CA2980461A patent/CA2980461C/en active Active
- 2016-04-15 ES ES16783103T patent/ES2767928T3/en active Active
- 2016-04-21 TW TW105112398A patent/TWI668908B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109604A (en) * | 2001-09-27 | 2003-04-11 | Matsushita Electric Ind Co Ltd | Gas diffusion electrode for fuel cell and method of manufacturing the same |
| CN101053101A (en) * | 2004-08-25 | 2007-10-10 | 通用汽车公司 | Diffusion media with microporous layer |
| CN103081194A (en) * | 2010-08-27 | 2013-05-01 | 东邦泰纳克丝株式会社 | Conductive sheet and production method for same |
| CN103563143A (en) * | 2011-06-17 | 2014-02-05 | 日产自动车株式会社 | Gas diffusion layer for fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016171082A1 (en) | 2016-10-27 |
| TW201703327A (en) | 2017-01-16 |
| KR102587488B1 (en) | 2023-10-11 |
| KR20170141710A (en) | 2017-12-26 |
| EP3288106B1 (en) | 2019-12-11 |
| JPWO2016171082A1 (en) | 2017-05-18 |
| CN107534156B (en) | 2020-11-27 |
| EP3288106A4 (en) | 2018-09-19 |
| US20180102552A1 (en) | 2018-04-12 |
| JP6135826B2 (en) | 2017-05-31 |
| EP3288106A1 (en) | 2018-02-28 |
| ES2767928T3 (en) | 2020-06-19 |
| US10680250B2 (en) | 2020-06-09 |
| CA2980461A1 (en) | 2016-10-27 |
| CA2980461C (en) | 2023-05-16 |
| TWI668908B (en) | 2019-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102121822B1 (en) | Gas-diffusion electrode base material for fuel cell | |
| JP6287490B2 (en) | Polymer electrolyte fuel cell | |
| JP6070889B2 (en) | Carbon sheet, gas diffusion electrode substrate and fuel cell | |
| JP6489009B2 (en) | Gas diffusion electrode substrate | |
| CN107078308B (en) | Gas diffusion electrode base material and method for producing gas diffusion electrode base material | |
| TWI692143B (en) | Carbon flake, gas diffusion electrode base material and fuel cell | |
| KR102120691B1 (en) | Gas diffusion electrode substrate, and membrane electrode assembly and fuel cell provided therewith | |
| CN109314252A (en) | Gas-diffusion electrode and fuel cell | |
| CN108370039A (en) | Gas-diffusion electrode and fuel cell | |
| TWI794685B (en) | Gas Diffusion Layers for Fuel Cells | |
| WO2019107241A1 (en) | Micro-porous layer and manufacturing method therefor, gas diffusion electrode substrate, and fuel battery | |
| CN107534156A (en) | Gas-diffusion electrode base material and its manufacture method | |
| CN110168788A (en) | Gas-diffusion electrode and fuel cell | |
| KR20180053680A (en) | Gas diffusion electrode and manufacturing method thereof | |
| CN108370040A (en) | Gas-diffusion electrode and fuel cell | |
| JP2017202948A (en) | Carbon sheet, gas diffusion electrode base material, and fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |